Polymer compositions with improved property constrancy

ABSTRACT

The invention provides polymer compositions of special graft rubber polymers, in the production of which are employed rubbers with defined particle diameters obtained by seed polymerisation using seed latex particles with defined particle diameters.

[0001] ABS moulding compositions or moulding compositions of the ABStype have already been used for many years in large amounts asthermoplastic resins for producing moulded parts of all types. In thisconnection the property spectrum of these resins can be varied withinwide ranges.

[0002] Particularly important properties of ABS moulding compositionsthat may be mentioned include toughness (impact strength, notched impactstrength) modulus of elasticity, processability (MVR), heat resistance,surface gloss, attention being paid to specific property combinationsdepending on the area of use.

[0003] A particularly important feature for the processing of ABSmoulding compositions, particularly when using fully automatedproduction plants, is the constancy of the properties or propertycombinations of the moulding compositions to be processed.

[0004] Although products with relatively narrow tolerance limits can beproduced by using modem processes in the ABS production (for examplecomputerised control of polymerisation and compounding), neverthelessfor special applications it is necessary to have even more improvedconstant properties that can be achieved only via the productcomposition or the product structure.

[0005] The object therefore existed of producing thermoplastic mouldingcompositions of the ABS type that exhibit from batch to batch veryconstant values for the most important properties also in the case ofvariations in the individual components that are used. The objectaccording to the invention is achieved by using combinations of specialgraft rubber polymers in the production of which are employed rubberswith defined particle diameters obtained by seed polymerisation usingseed latex particles with defined particle diameters.

[0006] The invention provides polymer compositions containing

[0007] I) at least one graft rubber polymer obtained by emulsionpolymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to50:50, styrene and/or acrylonitrile being able to be partially orcompletely replaced by α-methylstyrene, methyl methacrylate orN-phenylmaleimide or mixtures thereof, in the presence of a butadienepolymer latex (A) with a mean particle diameter d₅₀ of 230 to 330 nm,preferably 240 to 320 nm, and particularly preferably 250 to 310 nm,

[0008] II) at least one graft rubber polymer obtained by emulsionpolymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to50:50, styrene and/or acrylonitrile being able to be completely orpartially replaced by α-methyl-styrene, methyl methacrylate orN-phenylmaleimide or mixtures thereof, in the presence of a butadienepolymer latex (B) with a mean particle diameter d₅₀ of 340 to 480 nm,preferably 350 to 470 nm, and particularly preferably 360 to 460 nm,optionally

[0009] III) at least one graft rubber polymer obtained by emulsionpolymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to50:50, wherein styrene and/or acrylonitrile can be wholly or partiallyreplaced by α-methyl styrene, methyl methacrylate or N-phenylmaleimideor mixtures thereof, in the presence of a butadiene polymer latex (C)and

[0010] IV) at least one rubber-free copolymer of styrene andacrylonitrile in a weight ratio of 95:5 to 50:50, wherein styrene and/oracrylonitrile can be wholly or partially replaced by a-methyl styrene,methyl methacrylate or N-phenyl-maleimide or mixtures thereof

[0011] characterised in that the butadiene polymer latices (A) and (B)are obtained by seed polymerisation using at least one butadiene polymerlatex (C) with a mean particle diameter of 10 to 220 nm, preferably 20to 210 nm and particularly preferably 30 to 200 nm as seed latex, andthe graft rubber component III) is obtained by graft polymerisation inthe presence of at least one butadiene polymer latex (C) used as seedlatex for (A) and (B).

[0012] The present invention also provides a process for producing thepolymer compositions according to the invention wherein the butadienepolymer latices (A) and (B) are obtained by seed polymerisation using atleast one butadiene polymer latex (C) having a mean particle diameter of10 to 220 nm as a seed latex and the graft rubber component III) isobtained by graft polymerisation in the presence of at least onebutadiene polymer latex (C) used as seed latex for (A) and (B).

[0013] In general the polymer compositions according to the inventionmay contain the graft rubber components (I) and (II) and optionally(III) in arbitrary amounts, preferably in amounts of 1 to 60 parts byweight, particularly preferably in amounts of 5 to 50 parts by weight,and the rubber-free resin component (IV) preferably in amounts of 40 to99 parts by weight, particularly preferably in amounts of 50 to 95 partsby weight.

[0014] The weight ratio of (I):(II):(III) may be varied within widelimits; normally the weight ratio of (I):(II) is 90:10 to 10:90,preferably 80:20 to 20:80 and particularly preferably 70:30 to 35:65,and when (III) is used in addition the weight ratio [(I)+(II)]:(III) is10:90 to 80:20, preferably 20:80 to 70:30, and particularly preferably25:75 to 65:35.

[0015] Apart from the aforementioned polymer components the polymercompositions according to the invention may contain further rubber-freethermoplastic resins not built up from vinyl monomers, thesethermoplastic resins being used in amounts of up to 1000 parts byweight, preferably up to 700 parts by weight and particularly preferablyup to 500 parts by weight (in each case referred to 100 parts by weightof I+II+III+IV).

[0016] The butadiene polymer latices (A), (B) and (C) are produced byemulsion polymerisation of butadiene according to the so-called seedpolymerisation technique, in which first of all a finely particulatepolymer, preferably a butadiene polymer, is produced as seed latex andis then polymerised further with butadiene-containing monomers intolarger particles (see for example in Houben-Wyl, Methoden derOrganischen Chemie, Makromolekulare Stoffe, Part 1, p. 339 (1961),Thieme Verlag Stuttgart). In this connection the process is preferablycarried out using a seed batch process or a continuous seed flowprocess.

[0017] As comonomers there may be used up to 50 wt. % (referred to thetotal amount of monomer used for the butadiene polymer production) ofone or more monomers copolymerisable with butadiene.

[0018] Examples of such monomers include isoprene, chloroprene,acrylonitrile, styrene, α-methyl styrene, C₁-C₄-alkylstyrenes,C₁-C₈-alkyl acrylates, C₁-C₈-alkyl meth-acrylates, alkylene glycoldiacrylates, alkylene glycol dimethacrylates, divinyl benzene; butadieneis preferably used alone or mixed with up to 20 wt. %, preferably withup to 10 wt. %, of styrene and/or acrylonitrile.

[0019] As seed latex polymers there are preferably used butadienepolymers such as polybutadiene, butadiene/styrene copolymers,butadiene/acrylonitrile copolymers, or polymers obtained from theaforementioned monomers.

[0020] In principle there may also be used other finely particulatelatex polymers, for example polystyrene or styrene copolymers,poly(methyl methacrylate) or methyl methacrylate copolymers, as well aspolymers of other vinyl monomers.

[0021] Preferred seed latex polymers are polybutadiene latices.

[0022] In this connection seed latices (C) with a mean particle diameterd₅₀ of 10 to 220 nm, preferably 20 to 210 nm and particularly preferably30 to 200 nm are used in the production of the butadiene polymer latex(A) and butadiene polymer latex (B).

[0023] When using seed latices (C) with mean particle diameters d₅₀above 80 nm, preferably above 90 nm and particularly preferably above100 nm, the seed latices (C) themselves may also preferably be producedby seed polymerisation. For this purpose there are preferably used seedlatices (D) with mean particle diameters d₅₀ of 10 to 60 nm, preferably20 to 50 nm.

[0024] The butadiene polymer latex (A) has a mean particle diameter d₅₀of 230 to 330 nm, preferably 240 to 320 nm and particularly preferably250 to 310 nm.

[0025] The gel content of (A) is 30 to 80 wt. %, preferably 40 to 75 wt.% and particularly preferably 45 to 70 wt. %.

[0026] The butadiene polymer latex (B) has a mean particle diameter d₅₀of 340 to 480 nm, preferably 350 to 470 nm, and particularly preferably360 to 460 nm.

[0027] The gel content of (B) is 50 to 95 wt. %, preferably 55 to 90 wt.%, and particularly preferably 60 to 85 wt. %.

[0028] The butadiene polymer latex (C) has a mean particle diameter d₅₀of 10 to 220 nm, preferably 20 to 210 nm, and particularly preferably 30to 200 nm.

[0029] The gel content of (C) is 30 to 98 wt. %, preferably 40 to 95 wt.%, and particularly preferably 50 to 92 wt. %.

[0030] The seed latex (D), preferably a butadiene polymer latex, has amean particle diameter d₅₀ of 10 to 60 nm, preferably 20 to 50 nm.

[0031] The gel content of (D) is 10 to 95 wt. %, preferably 20 to 90 wt.%, and particularly preferably 30 to 85 wt. %.

[0032] The mean particle diameter d₅₀ may be determined byultracentrifuge measurements (see W. Scholtan, H. Lange: Kolloid Z. & Z.Polymere 250, p. 782 to 796 (1972)), the specified values for the gelcontent referring to the determination according to the wire cage methodin toluene (see Houben-Weyl, Methoden der Organischen Chemie,Makromolekulare Stoffe, Part 1, p. 307 (1961), Thieme Verlag Stuttgart).

[0033] The gel contents of the butadiene polymer latices (A), (B), (C)and (D) may in principle be adjusted in a manner known per se byemploying suitable reaction conditions (e.g. high reaction temperatureand/or polymerisation up to a high conversion, as well as optionally theaddition of crosslinking substances in order to achieve a high gelcontent, or for example low reaction temperature and/or termination ofthe polymerisation reaction before too high a degree of crosslinking hasoccurred, as well as optionally the addition of molecular weightregulators, such as for example n-dodecyl mercaptan or t-dodecylmercaptan in order to achieve a low gel content). As emulsifiers theremay be used conventional anionic emulsifiers such as alkyl sulfates,alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturatedfatty acids, as well as alkaline disproportionated or hydrogenatedabietinic acid or tall oil acid, and preferably emulsifiers are usedcontaining carboxyl groups (e.g. salts of C₁₀-C₁₈ fatty acids,disproportionated abietinic acid, emulsifiers according to DE-OS 36 39904 and DE-OS 39 13 509).

[0034] The preparation of the graft rubber polymers (I), (II) and (III)may be carried out in any appropriate manner by separate grafting of thebutadiene polymer latices (A), (B) and (C) in separate reactions or byjoint grafting of arbitrary mixtures selected from the butadiene polymerlatices (A), (B) and (C) during one reaction or two reactions or threereactions.

[0035] In this connection the graft polymerisation(s) may be carried outaccording to any suitable processes but is/are preferably carried out insuch a way that the monomer mixture is continuously added to thebutadiene polymer latex (A) and/or to the butadiene polymer latex (B)and/or to the butadiene polymer latex (C) and/or to arbitrary mixturesselected from the butadiene polymer latices (A), (B) and (C), and ispolymerised.

[0036] In this connection special monomer/rubber ratios are preferablymaintained and the monomers are added in a manner known per se to therubber.

[0037] In order to produce the components (I), (II) and (III) accordingto the invention, preferably 15 to 50 parts by weight, particularlypreferably 20 to 40 parts by weight, of a mixture of styrene andacrylonitrile that may optionally contain up to 50 wt. % (referred tothe total amount of the monomers used in the graft polymerisation) ofone or more monomers, are polymerised in the presence of 50 to 85 partsby weight, preferably 60 to 80 parts by weight (in each case referred tosolids) of the butadiene polymer latex (A) and/or of the butadienepolymer latex (B) and/or of the butadiene polymer latex (C) and/orarbitrary mixtures selected from the butadiene polymer latices (A), (B),and (C).

[0038] The monomers used in the graft polymerisation are preferablymixtures of styrene and acrylonitrile in a weight ratio of 95:5 to50:50, particularly preferably in a weight ratio of 80:20 to 65:35,wherein styrene and/or acrylonitrile may be wholly or partially replacedby copolymerisable monomers, preferably by α-methylstyrene, methylmethacrylate or N-phenylmaleimide. In principle arbitrary furthercopolymerisable vinyl monomers may additionally be used in amounts of upto ca. 10 wt. % (referred to the total amount of the monomers).

[0039] In addition molecular weight regulators may be used in the graftpolymerisation, preferably in amounts of 0.01 to 2 wt. %, particularlypreferably in amounts of 0.05 to 1 wt. % (in each case referred to thetotal amount of monomers in the graft polymerisation stage).

[0040] Suitable molecular weight regulators are for example alkylmercaptans such as n-dodecyl mercaptan, t-dodecyl mercaptan; dimericα-methylstyrene; terpinolene.

[0041] Suitable initiators that may be used include inorganic andorganic peroxide, e.g. H₂O₂, di-tert.-butyl peroxide, cumenehydroperoxide, dicyclohexyl percarbonate, tert.-butyl hydroperoxide,p-menthane hydroperoxide, azo initiators such as azobisisobutyronitrile,persalts such as ammonium, sodium or potassium persulfate, potassiumperphosphate, sodium perborate, as well as redox systems. Redox systemsconsist as a rule of an organic oxidising agent and a reducing agent, inwhich connection heavy metal ions may in addition be present in thereaction medium (see Houben-Weyl, Methoden der Organischen Chemie, Vol.14/1, pp. 263 to 297).

[0042] The polymerisation temperature is in general 25° C. to 160° C.,preferably 40° C. to 90° C. Suitable emulsifiers are mentioned above.

[0043] The graft polymerisation may be carried out under normaltemperature conditions, i.e. isothermally; the graft polymerisation ishowever preferably carried out so that the temperature differencebetween the start and end of the reaction is at least 10° C., preferablyat least 15° C., and particularly preferably at least 20° C.

[0044] In order to produce the components I), II) and III) according tothe invention, the graft polymerisation may preferably be carried out bycontinuous addition of the monomers in such a way that 55 to 90 wt. %,preferably 60 to 80 wt. % and particularly preferably 65 to 75 wt. % ofthe total amount of monomers used in the graft polymerisation aremetered in during the first half of the overall time for metering in themonomers; the remaining proportion of the monomers is metered in withinthe second half of the overall time for metering in the monomers.

[0045] As rubber-free copolymers IV) there are preferably usedcopolymers of styrene and acrylonitrile in a weight ratio of 95:5 to50:50, in which connection styrene and/or acrylonitrile may be wholly orpartially replaced by α-methylstyrene, methyl methacrylate orN-phenylmaleimide.

[0046] Particularly preferred are copolymers IV) containing proportionsof incorporated acrylonitrile units of <30 wt. %.

[0047] These copolymers preferably have mean molecular weights{overscore (M)}_(w) of 20,000 to 200,000 and intrinsic viscosities [η]of 20 to 110 ml/g (measured in dimethyl-formamide at 25° C.).

[0048] Details concerning the production of these resins are describedfor example in DE-A 2 420 358 and DE-A 2 724 360. Vinyl resins producedby bulk polymerisation or solution polymerisation have proved to beparticularly suitable. The copolymers may be added alone or as anarbitrary mixture.

[0049] Apart from using thermoplastic resins built up from vinylmonomers, it is also possible to use polycondensates, for examplearomatic polycarbonates, aromatic polyester carbonates, polyesters orpolyamides as rubber-free copolymer in the moulding compositionsaccording to the invention. Suitable thermoplastic polycarbonates andpolyester carbonates are known (see for example DE-A 1 495 626, DE-A 2232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396,DE-A 3 077 934), which may be prepared for example by reacting diphenolsof the formulae (V) and (VI)

[0050] in which

[0051] A denotes a single bond C₁-C₅-alkylene, C₂-C₅-alkylidene,C₅-C₆-cyclo-alkylidene, —O—, —S—, —SO—, —SO₂— or —CO—,

[0052] R⁵ and R⁶ independently of one another denote hydrogen, methyl orhalogen, in particular hydrogen, methyl, chlorine or bromine,

[0053] R¹ and R² independently of one another denote hydrogen, halogen,preferably chlorine or bromine, C₁-C₈-alkyl, preferably methyl, ethyl,C₅-C₆-cycloalkyl, preferably cyclohexyl, C₆-C₁₀-aryl, preferably phenyl,or C₇-C₁₂-aralkyl, preferably phenyl-C₁-C₄-alkyl, in particular benzyl,

[0054] m is an integer from 4 to 7, preferably 4 or 5,

[0055] n is 0 or 1,

[0056] R³ and R⁴ may be selected individually for each X andindependently of one another denote hydrogen or C₁-C₆-alkyl, and

[0057] X denotes carbon,

[0058] with carbonic acid halides, preferably phosgene, and/or witharomatic dicarboxylic acid dihalides, preferably benzenedicarboxylicacid dihalides, by phase boundary polycondensation, or with phosgene bypolycondensation in the homogeneous phase (so-called pyridine process),in which connection the molecular weight may be adjusted in a mannerknown per se by adding an appropriate amount of known chain terminators.

[0059] Suitable diphenols of the formulae (V) and (VI) are for examplehydroquinone, resorcinol, 4,4′-dihydroxydiphenyl,2,2-bis-(4-hydroxyphenyl)-propane,2,4-bis-(4-hydroxyphenyl)-2-methylbutane,2,2-bis-(4-hydroxy-3,5-dimethylphenyl)-propane,2,2-bis-(4-hydroxy-3,5-dichlorophenyl)-propane,2,2-bis-(4-hydroxy-3,5-dibromo-phenyl)-propane,1,1-bis-(4-hydroxyphenyl)-cyclohexane,1,1-bis-(4-hydroxy-phenyl)-3,3,5-trimethylcyclohexane,1,1-bis-(4-hydroxyphenyl)-3,3-dimethylcyclo-hexane,1,1-bis-(4-hydroxyphenyl)-3,3,5,5-tetramethylcyclohexane or1,1-bis-(4-hydroxyphenyl)-2,4,4,-trimethylcyclopentane.

[0060] Preferred diphenols of the formula (V) are2,2-bis-(4-hyroxyphenyl)-propane and1,1-bis-(4-hydroxyphenyl)-cyclohexane, and the preferred phenol of theformula (VI) is 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0061] Mixtures of diphenols may also be used.

[0062] Suitable chain terminators are for example phenol,p-tert.-butylphenol, long-chain alkyl phenols such as4-(l,3-tetramethylbutyl)phenol according to DE-A 2 842 005,monoalkylphenols, dialkylphenols having a total of 8 to 20 C atoms inthe alkyl substituents according to DE-A 3 506 472, such asp-nonylphenol, 2,5-di-tert.-butyl-phenol, p-tert.-octylphenol,p-dodecylphenol, 2-(3,5-dimethylheptyl)-phenol and4-(3,5-dimethylheptyl)-phenol. The necessary amount of chain terminatorsis generally 0.5 to 10 mole % referred to the sum of the diphenols (V)and (VI).

[0063] The suitable polycarbonates or polyester carbonates may be linearor branched; preferred products are preferably obtained by incorporating0.05 to 2.0 mole %, referred to the sum of the diphenols employed, oftrifunctional or higher functionality compounds, for example thosehaving three or more than three phenolic OH groups.

[0064] The suitable polycarbonates or polyester carbonates may containaromatically bound halogen, preferably bromine and/or chlorine; however,they are preferably halogen-free.

[0065] The polycarbonates and polyester carbonates have mean molecularweights ({overscore (M)}_(w), weight average), determined for example byultracentrifugation or light scattering measurements, of 10,000 to200,000, preferably 20,000 to 80,000.

[0066] Suitable thermoplastic polyesters are preferably polyalkyleneterephthalates, i.e. reaction products of aromatic dicarboxylic acids ortheir reactive derivatives (e.g. dimethyl esters or anhydrides) withaliphatic, cycloaliphatic or arylaliphatic diols and mixtures of suchreaction products.

[0067] Preferred polyalkylene terephthalates can be prepared fromterephthalic acids (or their reactive derivatives) and aliphatic orcycloaliphatic diols with 2 to 10 C atoms according to known methods(Kunststoff-Handbuch, Vol. VIII, p. 695 et seq. Carl Hanser Verlag,Munich 1973).

[0068] In preferred polyalkylene terephthalates 80 to 100 mole %,preferably 90 to 100 mole % of the dicarboxylic acid residues areterephthalic acid residues, and 80 to 100 mole %, preferably 90 to 100mole % of the diol residues are ethylene glycol residues and/orbutanediol-1,4 residues.

[0069] The preferred polyalkylene terephthalates may in addition toethylene glycol residues and/or butanediol-1,4 residues also contain 0to 20 mole % of residues of other aliphatic diols with 3 to 12 C atomsor cycloaliphatic diols with 6 to 12 C atoms, for example residues ofpropanediol-1,3, 2-ethylpropanediol-1,3, neopentyl glycol,pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4,3-methylpentanediol-1,3 and -1,6, 2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, hexanediol-2,5,1,4-di(β-hydroxyethoxy)-benzene, 2,2-bis-4-(hydroxycyclohexyl)-propane,2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane,2,2-bis-(3-β-hydroxyethoxyphenyl)-propane and2,2-bis-(4-hydroxypropoxyphenyl)-propane (DE-OS 2 407 647, 2 407 776, 2715 932).

[0070] The polyalkylene terephthalates may be branched by incorporatingrelatively small amounts of trihydroxy or tetrahydroxy alcohols or3-basic or 4-basic carboxylic acids, as are described in DE-OS 1 900 270and in U.S. Pat. No. 3,692,744. Examples of preferred branching agentsare trimesic acid, trimellitic acid, trimethylol ethane and trimethylolpropane, and pentaerythritol. It is advisable to use not more than 1mole % of the branching agent, referred to the acid component.

[0071] Particularly preferred are polyalkylene terephthalates that havebeen produced solely from terephthalic acid and its reactive derivatives(for example its dialkyl esters) and ethylene glycol and/orbutanediol-1,4, and mixtures of these polyalkylene terephthalates.

[0072] Preferred polyalkylene terephthalates are also copolyesters thathave been prepared from at least two of the abovementioned alcoholcomponents: particularly preferred copolyesters arepoly(ethyleneglycolbutanediol-1,4)-terephthalates.

[0073] The preferably suitable polyalkylene terephthalates generallyhave an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.3dl/g, in particular 0.6 to 1.2 dl/g, measured in each case inphenol/o-dichlorobenzene (1:1 parts by weight) at 25° C.

[0074] Suitable polyamides are known homopolyamides, copolyamides andmixtures of these polyamides. These polyamides may be partiallycrystalline and/or amorphous.

[0075] Suitable partially crystalline polyamides are polyamide-6,polyamide-6,6, mixtures and corresponding copolymers prepared from thesecomponents. Also suitable are partially crystalline polyamides whoseacid component consists wholly or partially of terephthalic acid and/orisophthalic acid and/or cork acid and/or sebacic acid and/or azelaicacid and/or adipic acid and/or cyclohexanedicarboxylic acid, whosediamine component consists wholly or partially of m- and/or p-xylylenediamine and/or hexamethylene diamine and/or 2,2,4-trimethylhexamethylenediamine and/or 2,2,4-trimethylhexamethylene diamine and/or isophoronediamine, and whose composition is in principle known.

[0076] There may also be mentioned polyamides that have been producedwholly or partially from lactams with 7 to 12 C atoms in the ring,optionally with the co-use of one or more of the abovementioned startingcomponents.

[0077] Particularly preferred partially crystalline polyamides arepolyamide-6 and polyamide-6,6 and their mixtures. As amorphouspolyamides there may be used known products that are obtained bypolycondensation of diamines such as ethylene diamine, hexamethylenediamine, decamethylene diamine, 2,2,4- and/or2,4,4-trimethylhexamethylene diamine, m- and/or p-xylylene diamine,bis-(4-amino-cyclohexyl)-methane, bis-(4-aminocyclohexyl)-propane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane,3-aminomethyl-3,5,5,-trimethylcyclohexylamine, 2,5- and/or2,6-bis-(aminomethyl)-norbornane and/or 1,4-diaminomethylcyclohexanewith dicarboxylic acids such as oxalic acid, adipic acid, azelaic acid,decanedicarboxylic acid, heptadecanedicarboxylic acid, 2,2,4- and/or2,4,4-trimethyladipic acid, isophthalic acid and terephthalic acid.

[0078] Also suitable are copolymers obtained by polycondensation ofseveral monomers, as well as copolymers prepared with the addition ofaminocarboxylic acids such as ε-aminocaproic acid, ω-aminoundecanoicacid or ω-aminolauric acid or their lactams.

[0079] Particularly suitable amorphous polyamides are the polyamidesprepared from isophthalic acid, hexamethylene diamine and furtherdiamines such as 4,4′-diamino-dicyclohexylmethane, isophorone, 2,2,4-and/or 2,4,4-trimethylhexamethylene diamine, 2,5- and/or2,6-bis-(aminomethyl)-nobornane; or from isophthalic acid,4,4′-diaminodicyclohexylmethane and 6ε-caprolactam; or from isophthalicacid, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane and laurinlactam; orfrom terephthalic acid and the isomeric mixture of 2,2,4- and/or2,4,4-trimethylhexamethylene diamine.

[0080] Instead of the pure 4,4′-diaminodicyclohexylmethane, mixtures ofthe positional isomeric diaminodicyclohexylmethanes that are composed ofthe following components may also be used

[0081] 70 to 99 mole % of the 4,4′-diamino isomer

[0082] 1 to 30 mole % of the 2,4′-diamino isomer

[0083] 0 to 2 mole % of the 2,2′-diamino isomer, and

[0084] optionally correspondingly higher condensed diamines that areobtained by hydrogenating industrial quality diaminodiphenylmethane. Theisophthalic acid may be replaced in an amount of up to 30% byterephthalic acid.

[0085] The polyamides preferably have a relative viscosity (measured ina 1 wt. % solution in m-cresol at 25° C.) of 2.0 to 5.0, particularlypreferably 2.5 to 4.0.

[0086] Preferred moulding compositions according to the inventioncontain 1 to 60 parts by weight, preferably 5 to 50 parts by weight ofthe graft polymer components I), II) and III), and 40 to 99 parts byweight, preferably 50 to 95 parts by weight, of rubber-free copolymer.

[0087] The production of the moulding compositions according to theinvention is carried out by mixing the components I), II) and III) andIV) in conventional mixing units (preferably in multiple roll mills,mixing extruders or internal kneaders).

[0088] The invention accordingly also provides a process for producingthe moulding compositions according to the invention, wherein thecomponents I), II) and III) and IV) are mixed and compounded at elevatedtemperature, in general at temperatures of 150° C. to 300° C., and arethen extruded.

[0089] Necessary and/or advantageous additives, for exampleantioxidants, UV stabilisers, peroxide destroyers, antistatic agents,lubricating agents, mould release agents, flame protection agents,fillers or reinforcing materials (glass fibres, carbon fibres etc.) andpigments may be added to the moulding compositions according to theinvention during the production, processing, further processing andfinal shaping stages.

[0090] The final shaping may be carried out in conventional processingunits, and includes for example processing by injection moulding, sheetextrusion optionally followed by heat forming, cold forming, extrusionof pipes and profiled sections, and calender processing.

[0091] In the following examples the specified parts are always parts byweight and the specified % are always wt. % unless otherwise stated.

EXAMPLES Components

[0092] ABS Graft Polymer 1 (According to the Invention)

[0093] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 289mn and a gel content of 66 wt. %, produced by free-radical seedpolymerisation using a polybutadiene seed latex with a mean particlediameter d₅₀ of 118 nm, and 29 parts by weight (calculated as solids) ofan anionically emulsified polybutadiene latex with a mean particlediameter d₅₀ of 399 mn and a gel content of 80 wt. % and produced byfree-radical seed polymerisation using a polybutadiene seed latex with amean particle diameter d₅₀ of 137 nm, are adjusted with water to asolids content of ca. 20 wt. %, heated to 59° C., following which 0.5part by weight of potassium peroxodisulfate (dissolved in water) isadded.

[0094] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0095] ABS Graft Polymer 2 (According to the Invention) 29 parts byweight (calculated as solids) of an anionically emulsified polybutadienelatex with a mean particle diameter d₅₀ of 289 nm and a gel content of66 wt. %, produced by free-radical seed polymerisation using apolybutadiene latex with a mean particle diameter d₅₀ of 118 nm, and 29parts by weight (calculated as solids) of an anionically emulsifiedpolybutadiene latex with a mean particle diameter d₅₀ of 410 nm and agel content of 85 wt. % produced by free-radical seed polymerisationusing a polybutadiene seed latex with a mean particle diameter d₅₀ of118 nm, are adjusted with water to a solids content of ca. 20 wt. %,then heated to 59° C., following which 0.5 part by weight of potassiumperoxodisulfate (dissolved in water) is added.

[0096] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0097] ABS Graft Polymer 3 (According to the Invention)

[0098] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 289nm and a gel content of 66 wt. %, produced by free-radical seedpolymerisation using a polybutadiene latex with a mean particle diameterd₅₀ of 118 nm, and 29 parts by weight (calculated as solids) of ananionically emulsified polybutadiene latex with a mean particle diameterd₅₀ of 456 nm and a gel content of 76 wt. % produced by free-radicalseed polymerisation using a polybutadiene seed latex with a meanparticle diameter d₅₀ of 137 nm, are adjusted with water to a solidscontent of ca. 20 wt. %, heated to 59° C., following which 0.5 part byweight of potassium peroxodisulfate (dissolved in water) is added.

[0099] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0100] ABS Graft Polymer 4 (According to the Invention)

[0101] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 289nm and a gel content of 66 wt. %, produced by free-radical seedpolymerisation using a polybutadiene seed latex with a mean particlediameter d₅₀ of 118 nm, and 29 parts by weight (calculated as solids) ofan anionically emulsified polybutadiene latex with a mean particlediameter d₅₀ of 445 nm and a gel content of 84 wt. % produced byfree-radical seed polymerisation using a polybutadiene seed latex with amean particle diameter d₅₀ of 137 nm, are adjusted with water to asolids content of ca. 20 wt. %, heated to 59° C., following which 0.5part by weight of potassium peroxodisulfate (dissolved in water) isadded.

[0102] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0103] ABS Draft Polymer 5 (Comparison)

[0104] The “ABS graft polymer 1” instructions are repeated, wherein amixture of polybutadiene latices that have in each case been producedwithout using seed latex is employed (29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 299 nm and a gel content of 70 wt. %, and 29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 391 nm and a gel content of 80 wt. %).

[0105] ABS Draft Polymer 6 (Comparison)

[0106] The “ABS graft polymer 2” instructions are repeated, wherein amixture of polybutadiene latices that have in each case been producedwithout using seed latex is employed (29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 299 nm and a gel content of 70 wt. %, and 29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 416 nm and a gel content of 87 wt. %).

[0107] ABS Draft Polymer 7 (Comparison)

[0108] The “ABS graft polymer 3” instructions are repeated, wherein amixture of polybutadiene latices that have in each case been producedwithout using seed latex is employed (29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 282 nm and a gel content of 49 wt. %, and 29 parts by weight ofpolybutadiene latex (calculated as solids) with a mean particle diameterd₅₀ of 432 nm and a gel content of 81 wt. %).

[0109] ABS Graft Polymer 8 (According to the Invention)

[0110] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 305nm and a gel content of 55 wt. %, produced by free-radical seedpolymerisation using a polybutadiene latex with a mean particle diameterd₅₀ of 111 nm, and 29 parts by weight (calculated as solids) of ananionically emulsified polybutadiene latex with a mean particle diameterd₅₀ of 404 nm and a gel content of 81 wt. % produced by free-radicalseed polymerisation using a polybutadiene seed latex with a meanparticle diameter d₅₀ of 137 nm, are adjusted with water to a solidscontent of ca. 20 wt. %, heated to 59° C., following which 0.5 part byweight of potassium peroxodisulfate (dissolved in water) is added.

[0111] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0112] ABS Graft Polymer 9 (According to the Invention)

[0113] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 305nm and a gel content of 55 wt. %, produced by free-radical seedpolymerisation using a polybutadiene seed latex with a mean particlediameter d₅₀ of 111 nm, and 29 parts by weight (calculated as solids) ofan anionically emulsified polybutadiene latex with a mean particlediameter d₅₀ of 405 nm and a gel content of 75 wt. % produced byfree-radical seed polymerisation using a polybutadiene seed latex with amean particle diameter d₅₀ of 137 nm, are adjusted with water to asolids content of ca. 20 wt. %, heated to 59° C., following which 0.5part by weight of potassium peroxodisulfate (dissolved in water) isadded.

[0114] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0115] ABS Graft Polymer 10 (According to the Invention)

[0116] 29 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 305nm and a gel content of 55 wt. %, produced by free-radical seedpolymerisation using a polybutadiene seed latex with a mean particlediameter d₅₀ of 111 nm, and 29 parts by weight (calculated as solids) ofan anionically emulsified polybutadiene latex with a mean particlediameter d₅₀ of 412 nm and a gel content of 84 wt. % produced byfree-radical seed polymerisation using a polybutadiene seed latex with amean particle diameter d₅₀ of 137 nm, are adjusted with water to asolids content of ca. 20 wt. %, heated to 59° C., following which 0.5part by weight of potassium peroxodisulfate (dissolved in water) isadded.

[0117] 42 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.12 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0118] ABS Graft Polymer 11 (According to the Invention)

[0119] 50 parts by weight (calculated as solids) of an anionicallyemulsified polybutadiene latex with a mean particle diameter d₅₀ of 137nm and a gel content of 88 wt. %, produced by free-radical seedpolymerisation using a polybutadiene seed latex with a mean particlediameter d₅₀ of 48 nm are adjusted with water to a solids content of ca.20 wt. %, heated to 59° C., following which 0.5 part by weight ofpotassium peroxodisulfate (dissolved in water) is added.

[0120] 50 parts by weight of a mixture of 73 wt. % of styrene, 27 wt. %of acrylonitrile and 0.15 part by weight of tert.-dodecyl mercaptan arethen metered in uniformly within 6 hours; parallel to this 1 part byweight (calculated as solids) of the sodium salt of a resin acid mixture(Dresinate 731, Abieta Chemie GmbH, Gersthofen, Germany, dissolved inalkaline adjusted water) is metered in over a period of 6 hours. Duringthe course of the 6 hours the reaction temperature is raised from 59° C.to 80° C. After a post-reaction time of 2 hours at 80° C. the graftlatex is coagulated, after adding ca. 1.0 part by weight of a phenolicantioxidant, with a magnesium sulfate/acetic acid mixture, and afterwashing with water the resultant moist powder is dried at 70° C.

[0121] Resin Component 1

[0122] Statistical styrene/acrylonitrile copolymer(styrene:acrylonitrile weight ratio 72:28) with a {overscore (M)}_(w) ofca. 115,000 and {overscore (M)}_(w)/{overscore (M)}_(n)−1≦2 obtained byfree-radical solution polymerisation.

[0123] Resin Component 2

[0124] Statistical styrene/acrylonitrile copolymer(styrene:acrylonitrile weight ratio 72:28) with a {overscore (M)}_(w) ofca. 85,000 and {overscore (M)}_(w)/{overscore (M)}_(n)−1≦2 obtained byfree-radical solution polymerisation.

[0125] Moulding Compositions

[0126] The aforedescribed polymer components are mixed in an internalkneader in the proportions given in Table 1 together with 2 parts byweight of ethylenediamine bisstearyl amide and 0.1 part by weight of asilicone oil and after granulation are processed into test pieces.

[0127] The following data are obtained:

[0128] notched impact strength at room temperature (a_(k) ^(RT)) and at−40° C. (a_(k) ^(−40° C.)) according to ISO 180/1A (unit: kJ/m²), ballindentation hardness (Hc) according to DIN 53 456 (unit: N/mm²),thermoplastic flow (MVI) according to DIN 53 735 U (unit: cm³/10 min).

[0129] It is clear from the Examples (test data see Table 2) that theproducts according to the invention exhibit very narrow fluctuationranges in the most important properties (in particular toughness andprocessability).

[0130] Although the comparison products exhibit similar absolute valuesfor the tested properties, the fluctuation ranges are however muchgreater. TABLE 1 Compositions of the moulding compositions ABS graftpolymer Resin Component 1 2 3 4 5 6 7 8 9 10 11 1 2 (parts (parts (parts(parts (parts (parts (parts (parts (parts (parts (parts (parts (partsExample by wt.) by wt.) by wt.) by wt.) by wt.) by wt.) by wt.) by wt.)by wt.) by wt.) by wt.) by wt.) by wt.)  1 40 — — — — — — — — — 60 —  2— 40 — — — — — — — — — 60 —  3 — 40 — — — — — — — — 60 —  4 — — 40 — — —— — — — 60 —  5 (Comparison) — — — 40 — — — — — — 60 —  6 (Comparison) —— — — 40 — — — — — 60 —  7 (Comparison) — — — — — 40 — — — — 60 —  8 — —— — — — 15 — — 15 — 70  9 — — — — — — — 15 — 15 — 70 10 15 15 — 70

[0131] TABLE 2 Test data of the moulding compositions a_(k) ^(RT) a_(k)^(−40° C.) Hc MVI Example (kJ/m²) (kJ/m²) (N/mm²) (cm³/ 10 min)  1 31.221.3 81 9.6  2 30.7 21.3 81 9.6  3 31.1 21.3 80 9.4  4 30.9 21.7 81 9.3 5 (Comparison) 31.1 19.9 81 7.5  6 (Comparison) 29.1 17.9 84 8.7  7(Comparison) 33.4 15.3 88 9.2  8 17.5 8.6 114 33.4  9 16.9 8.9 114 33.910 17.0 9.2 113 33.7

1. Polymer compositions comprising I) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, styrene and/or acrylonitrile being able to be partially or completely replaced by α-methylstyrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (A) with a mean particle diameter d₅₀ of 230 to 330 nm, II) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, styrene and/or acrylonitrile being able to be completely or partially replaced by α-methylstyrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (B) with a mean particle diameter d₅₀ of 340 to 480 nm, III) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, wherein styrene and/or acrylonitrile can be wholly or partially replaced by α-methyl styrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (C) and IV) at least one rubber-free copolymer of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50 wherein styrene and/or acrylonitrile can be wholly or partially replaced by α-methyl styrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, characterised in that the butadiene polymer latices (A) and (B) were obtained by seed polymerisation using at least one butadiene polymer latex (C) with a mean particle diameter of 10 to 220 nm as seed latex, and the graft rubber component III) was obtained by graft polymerisation in the presence of at least one butadiene polymer latex (C) used as seed latex for (A) and (B).
 2. Polymer compositions according to claim 1 comprising I) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, styrene and/or acrylonitrile being able to be partially or completely replaced by α-methylstyrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (A) with a mean particle diameter d₅₀ of 240 to 320 nm, II) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, styrene and/or acrylonitrile being able to be completely or partially replaced by α-methylstyrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (B) with a mean particle diameter d₅₀ of 350 to 470 nm, optionally III) at least one graft rubber polymer obtained by emulsion polymerisation of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50, wherein styrene and/or acrylonitrile can be wholly or partially replaced by α-methyl styrene, methyl methacrylate or N-phenylmaleimide or mixtures thereof, in the presence of a butadiene polymer latex (C) and IV) at least one rubber-free copolymer of styrene and acrylonitrile in a weight ratio of 95:5 to 50:50 wherein styrene and/or acrylonitrile can be wholly or partially replaced by α-methyl styrene, methyl methacrylate or N-phenyl-maleimide or mixtures thereof characterised in that the butadiene polymer latices (A) and (B) were obtained by seed polymerisation using at least one butadiene polymer latex (C) with a mean particle diameter of 20 to 210 nm as seed latex and the graft rubber component III) was obtained by graft polymerisation in the presence of at least one butadiene polymer latex (C) used as seed latex for (A) and (B).
 3. Polymer compositions according to claim 1, in addition at least one resin selected from an aromatic polycarbonate, aromatic polyester carbonate, polyester, polyamide or mixtures thereof.
 4. Polymer compositions according to claim 1, characterised in that in the production of the graft rubber polymers the monomer feed is carried out in such a way that 55 to 90 wt. % of all the monomers to be used in the graft polymerisation are metered in during the first half of the overall time for metering in the monomers and the remaining fraction of the monomers is metered in during the second half of the overall time for metering in the monomers.
 5. Polymer compositions according to claim 1 comprising characterised in that in the production of the graft rubber polymers the temperature difference between the start and end of the grafting reaction is at least 15° C.
 6. Process for producing the polymer compositions according to claim 1, wherein the butadiene polymer latices (A) and (B) are obtained by seed polymerisation using at least one butadiene polymer latex (C) with a mean particle diameter of 10 to 220 nm as seed latex and the graft rubber component III) is obtained by graft polymerisation in the presence of at least one butadiene polymer latex (C) used as seed latex for (A) and (B).
 7. Process for producing polymer compositions according to claim 1, characterised in that the components I), II) and optionally III) and IV) are mixed and then compounded and extruded at elevated temperature.
 8. Use of the polymer composition according to claim 1 for producing moulded parts.
 9. Moulded parts obtainable from polymer compositions according to claim
 1. 